Phthalimido esters of cyclopropanecarboxylic acid esters



3,268,551 PHTHALlMlDU ESTERS F @YCLUPROPANE- CARlstlXYLlC ACID ESTERSSaichiro Kuramoto, Toyonalra-shi, 'llalreaki Kato, Kenzo Ueda, andYositosi @lruno, Nishinomiya-shi, and Keimei Fujimoto, Minoo-shi, Japan,assignors to Sunritomo Chemical Company, Ltd, Higashi-lnr, Osaka, Japan,a corporation of Japan No Drawing. Original application July 30, 1963,Ser. No. 298,589. Divided and this application Dec. 18, 1964, Ser. No.424,875 Claims priority, application Japan, Aug. 6, 1962, $763,598,37/393,599; Oct. 3, 1962, 37/44,473, 37/4 1,474

13 Claims. (Cl. 26tl-325) This application is a division of ourco-pending application Serial No. 298,589, filed July 30, 1963.

This invention relates to novel cyclopropanecarboxylic acid esters, to aprocess for preparing the same, and to insecticidal compositionscontaining the same. More particularly, it relates to novelcyclopropanecarboxylic acid esters having the general formula,

wherein X X X and X each means a member selected from the groupconsisting of hydrogen and halogen atoms, methyl, nitro, methoxy, andcyano radicals, Z is a member of oxygen and sulfur atoms; Y is a memberof the group consisting of a direct linkage and alkylene residue havingcarbon number of l to 3; and R is a member selected from methyl andmethoxycarbonyl radicals; to a process for preparing the same; and toinsecticidal compositions containing the same.

It is one object of the invention to provide a novel group ofcyclopropanecarboxylic acid esters, particularly of chrysanthemumcarboxylic acid esters, which have strong insecticidal activities tohouse and agricultural insects with low toxicities to warm-bloodedanimals and plants, and which can be commercially produced in low cost.Another object is to provide a process for preparing such novel estersby a commercially available procedure. Still another object is toprovide insecticidal composition containing such an ester. Other objectswould be obvious from the following description.

As an insecticide utilizable with safety because of the harmlessness towarm-blooded animals, pyrethrum extract has long been employed.Recently, allethrin which is an analog of the effective ingredients inpyrethrum extract, i.e. pyrethrin and cinerin, was synthesized anddeveloped for insectical uses. These ingredients are surely valuable intheir high insecticidal powers, especially in their rapid effect toinsects, and in the characteristics of permitting no, or little,resistivity to insects. However, their uses are limited to some extentbecause of their complicated steps of the production and their greatexpense for the production.

The present inventors have made broad researches on the variouscyclopropanecarboxylic acid esters, and have now found the present novelgroup of cyclopropanecarboxylic acid esters, which possess significantinsecticidal power but are harmless to warm-blooded animals, and whichcan be prepared from easily available materials by a simple process withlow prices. In other words, the present componds are(thio)phthalimido(alkyl) esters of Chrysanthemum carboxylic acids.Accordingly, it is United States Patent 0 "ice a feature of the presentinvention that the characteristics of the present compounds resemble topyrethrin, cinerin and allethrin, even through the alcohol moieties ofthe former are extremely simple as compared to those of the latter andare composed of carbon, hydrogen, oxygen and nitrogen atoms, unlike thelatter composed of carbon, hydrogen and oxygen.

Thus, the present invention is to provide novel cyclopropanecarboxylicacid esters having the formula,

wherein X X X X Z, Y and R have the same meanings as identified above,and to provide a process for preparing such compounds, comprisingesterifying a phthalimide compound having the general formula,

I N-Y0H k wherein X X X X Z and Y have the same meaning as identifiedabove, with a cyclopropanecarboxylic acid having the general formula,

CH3 HOOCCHCH-CH=C R CH3 CH3 wherein R has the same meaning as identifiedabove, according to the general esterifying procedure.

The phthalimide compound employed in the present invention may beprepared from phthalic acid, phthalic anhydride, phthalimide, and theirnucleus-substituted compounds according to the conventional procedureswell-known to those skilled in the art.

The cyclop-ropanecarboxylic acid employed in the present invention iseither chrysanthem urn monocarlboxylic acid (R being CH or pyrethricacid (R being COOCH a monomethyl ester of chrysanthemum dicarboxylicacid). They are the acidic moieties of pyrethrin, cinerin and allethrin,and can be synthesized according to the known method.

The esterification reaction of the present invention may be effected invarious ways. The phthalimide compound may be heated with thecyclopropanecanboxylic acid in the presence of a strong acid, such asaromatic sulfonic acid and sulfuric acid, in an organic solvent capableof azeotropically boiling with water, thereby to remove the water formedin the esterification, out of the reaction system. It may also 'beheated with a lower alkyl ester of the cycloprop-anecarboxylic acid inthe presence of a basic catalyst, such as sodium and potassium, therebyto continuously remove the lower alcohol formed through theester-exchanging reaction out of the reaction system. In such case,methyl, ethyl, n-propyl and isopropyl ester are suitable. In the mostpreferable esterification, it may the treated with thecyclopropanecarboxylic acid halide in an inert. organic solvent,preferably in the presence of a de-hydrogen halide agent, whereby theesterification is proceeded with the isolation of a hydrohalic acid saltwithin a short period of time. In this case, the acid chloride is themost preferable, though the bromide and the iodide may be em ployable.Further, it may be refluxed with the cyclopropanecanboxylic acidanhydride in an inert solvent for several hours, thereby to yield theobjective ester and free cyclopropanecarboxylic acid, the latter beingrecov' ered and again converted to the anhydride by treatment with, forexample, acetic anhydride for reuse. Alternatively, the phthalimidecompound may be employed for the esterification in the form of thehalide having the general formula,

wherein X X X X Z and Y have the same meanings as identified above, andA means a halogen atom. In this case, the halide may be heated with analkali metal salt of the cyclopropanecanboxylic acid in an inertsolvent, thereby to yield the objective ester with the iso' lation of analkali metal halide salt. In the formula, A may be any of chlorine,bromine, and iodine, among which the former two are preferable andpractical. As the alkali metals, sodium and potassium are preferable.

As well-known, the cyclopropanecarboxylic acid as identified abovecomprises various stereoisomers and optical isomers. It is needless tosay that the acid and the derivatives thereof as described hereininvolve their isomers.

The process of the invention is described in more detail with referenceto the following examples, which are however to be construed tor thepurpose of illustration and not of the limitation.

EXAMPLE 1 To a mixture of 17.7 g. (0.1 mole) ofN-hydroxymethylphthalimide, 18 g. of chrysanthemum monocarboxylic acidand 100 ml. of dry benzene, is added 1 g. of p-toluenesulfonic acid. Themixture is refluxed to remove the resulting water azeotropically. Whenthe theoretical amount of water for the esterification is distilled off,the mixture is cooled and washed with an aqueous saturated sodiumbicarbonate solution to remove the acidic substance, and then with anaqueous saturated sodium chloride solution. The mixture is thendistilled to remove the solvent. "The residue is solidified, which isrecrystallized from lignoin, thereby to yield phthalirnidomethyl esterof chrysanthemum monocarboxylic acid, colorless scales, having M.P.110-l13 C., in yield of 26.2 g. (80%).

Analysis.-Calculated for (C H NO C, 69.70; H, 6.47; N, 4.28%. Found: C,69.72; H, 6.50; N, 4.24%.

EXAMPLE 2 A mixture of 17.7 g. (0.1 mole) of N-hydroxyrnethylphthalimideand 19.6 .g. of ethyl chrysanthemum monocarboxylate is heated at about150 C., and 0.3 g. of sodium is added to the heated mixture, wherebyethyl alcohol starts to be distilled out. When the distilling iscompleted, 0.3 g. of sodium is added again thereto. The addition isrepeated 7 times in total, whereby the theoretical amount of ethylalcohol for the esterification is distilled off. The mixture is thencooled, mixed with ethyl ether, washed with hydrochloric acid, with anaqueous saturated sodium bicarbonate solution and then with a saturatedsodium chloride solution, and dried over anhydrous sodium sulfate.Removal of the solvent from the mixture leaves 19.6 g. (60%) ofphthalimidomethyl ester of chrysanthemum monocarboxylic acid.

EXAMPLE 3 A mixture of 17.7 g. (0.1 mole) of N-hydroxymethylphthalimide,50 ml. of dry toluene and 50 g. of pyridine,

is cooled with ice, and a solution of 19 g. (1.02 moles) ofchrysanthemum monocarboxylic acid chloride dissolved in 50 ml. oftoluene is added to the mixture. Upon the addition, pyridiniumhydrochloride salt is isolated. After stirring at room temperature for 7hours, the mixture is filtered, and the filtrate is washed with a dilutehydrochloric acid solution to remove excess of pyridine, then washedwith an aqueous 5% sodium carbonate solution and with an aqueoussaturated sodium chloride, subsequently. Upon distillation of toluenefrom the mixture in vacuo, crystals of phthalimidomethyl ester ofchrysanthemum monocarboxylic acid is obtained, which has M.P. 1l0113 C.after a recrystallization from toluene. The yield is 27.8 g.

EXAMPLE 4 EXAMPLE 5 A dispersion of 19 g. (0.1 mole) of sodiumchrysanthemum monocarboxylate in a naphtha solvent is heated at about150 C., and 20g. of N-(chloromethyl)phthalimide is added thereto overabout 30 minutes. Esterification is proceeded with isolation of sodiumchloride. Removal of the solvent by distillation in vacuo leaves 21.2 g.(65%) of phthalirnidomethyl ester of chrysanthemum monocarboxylic acid.

EXAMPLE 6 A mixture of 21.2 g. (0.1 mole) of4-chloro-N-hydroxymethylphthalimide, 60 g. of pyridine and 50 ml. of drytoluene is treated with chrysanthemum monocarboxylic acid chloride as inExample 3, and 34.4 g. of 4-chlor0phthalimidomethyl ester ofchrysanthemum monocarboxylic acid is obtained. A recrystallization fromligroin yields colorless needles, M.P. 7983 C.

C1 CH3 CH3 CH Analysis.Calculated (for C H NO Cl): C, 62.98; H, 5.52; N,3.87%. Found C, 62.80; H, 5.79; N, 3.88%.

EXAMPLE 7 Using 25.6 g. (0.1 mole) of 4-bromo-N-hydroxymethylphthalimideand 19 'g. of chrysanthemum monocarboxylic acid chloride, the sameprocedure as in Example 3 is conducted, and 37.4 g. (92%) of yellow oily4-bromophthalimidomethyl ester of chrysanthemum monocarboxylic acid isobtained.

\ O O CO Alzalysis.--Calculated (for C H NO Br): C, 56.17; H, 4.96; Br,19.67%. Found: C, 56.23; H, 5.03; Br, 19.81%.

EXAMPLE 3 A mixture of 24.6 g. (0.1 mole) of 3,6-dichloro-N-hydroxymethylphthalimide, 60 g. of pyridine and 50 ml. of dry toluene,is treated with chrysanthemum monocarboxylic acid chloride as in Example3, and 36.0 g. (91%) of 3,6-dichlorophthalimidomethyl ester ofchrysanthemum noncarboxylic acid is obtained. A recrystallization fromligroin yields colorless needles, M.P. 120- 127 C.

Example 3 is conducted, and 43.3 g. (93%) of 3,4,5,6-tetrachlorophthalimidomethyl ester of chrysanthemum monocarboxylic acidis obtained.

I oo 01 CH CH Analysis-Calculated (for C H Cl NO,): C, 49.06; H, 3.63;Cl, 30.49%. Found: C, 49.11; H, 3.59; CI, 30.66%.

EXAMPLE Using 23.2 g. (0.1 mole) of 3-nitro-N-hydroxymethylphthalimideand 19 g. of chrysanthemum monocarboxylic acid chloride, the sameprocedure as in Example 3 is conducted, and 32.7 g. (88%) of3-nitrophthalimidomethyl ester of chrysanthemum monocarboxylic acid isobtained. A recrystallization from a mixed ligroin-toluene solventyields colorless needles, M.P. 118120 C.

Analysis-Calculated (for C H N O C, 61.29; H, 5.38; N, 7.53%. Found: C,61.35; H, 5.22; N, 7.55%.

EXAMPLE 11 Using 23.2 g. (0.1 mole) of4-nitro-N-hydroxymethylphthalimidomethyl ester of chrysanthemummonoca'racid chloride, the same procedure as in Example 3 is conducted,and 35.0 g. (90%) of 4-nitrophthalimidomethyl ester of chrysanthemummonocarboxylic acid is obtained. A recrystallization from a mixedligroin-toluene solvent yields colorless needles, M.P. 125-130" C.

C II; C H

6 Analysis.-Calculated (for C H N O C, 61.29; H, 5.38; N, 7.53%. Found:C, 61.40; H, 6.06; N, 7.50%.

EXAMPLE 12 Using 30.1 g. (0.1 mole) of3-bromo-6-nitro-N-hydroxymethylphthalimide and 19 g. of chrysanthemummonocarboxylic acid chloride, the same ester'ification as in Example 3is conducted, and 40.6 g. (90.0%) of yellow oily3-bromo--nitrophthalimidomethyl ester of chrysanthemum monocarboxylicacid is obtained.

Analysis-Calculated (for C H BrN O C, 50.57;

H, 4.24; Br, 17.71%. Found: C, 50.83; H, 4.44; Br, 17.94%.

EXAMPLE 13 Using 19.1 g. (0.1 mole) of3-methyl-N-hydroxymethylphthalimide and 19 g. of chrysanthemummonocarboxylic acid chloride, the same esterification as in Example 3 isconducted, and 32.7 g. (96%) of oily 3-methylphthalimidomethyl ester ofchrysanthemum monocarboxylic acid is obtained.

I CO CH3 Analysis-Calculated (for C I-I NO C, 70.36; H, 6.79; N, 4.10%.Found: C, 70.50; H, 6.69; N, 4.35%.

EXAMPLE 14 Using 19.1 g. (0.1 mole) of4methy1-N-hydroxymethylphthalimide and 19 g. of chrysanthemummonocarboxylic acid chloride, the same esterification as in Example 3 isconducted, and 32.4 g. of oily 4- methylphthalimidomethyl ester ofchrysanthemum monocarboxylic acid is obtained.

CH CH3 CH CH Analysis.Calculated (for C H NO C, 70.36; H, 6.79; N,4.10%. Found: C, 70.90; H, 6.58; N, 4.01%.

EXAMPLE 15 Using 20.7 g. (0.1 mole) of4-methoxy-N-hydroxymethylphthalimide and 19 g. of chrysanthemum.monocarboxylic acid chloride, the same esterification as in Example 3 isconducted, and 33.2 g. (93%) of pale yellow oily4-1nethoxyphthalimidomethyl ester of chrysanthemum monocarboxylic acidis obtained.

\CO CH3 Analysis.Calculated (for C2OH22NO5): c, 67.21; H, 6.49; N,3.92%. Found: c, 68.00; H, 6.52; N, 4.10%.

EXAMPLE 16 Using 24.2 g. of3-chloro-4-methoxy-N-hydroxymethylphthalimide and 19 g. of chrysanthemummonocarboxylic '7 acid chloride, the same esterification as in Example 3is conduced, and 37.6 g. (96%) of pale yellow oily 3-chloro-4-methoxyphthalimidomethyl ester of chrysanthe-mum monocarboxylicacid is obtained.

Analysis.-Calculated (for C H ClNO C, 61.30;

H, 5.66; Cl, 9.05%. 9.01%.

Found: C, 61.40; H, 6.02; Cl,

EXAMPLE 17 Using 20.2 g. (0.1 mole) of4-cyano-N-hydroxymethylphthalimide and 19 g. of chrysanthemummonocarboxylic acid chloride, the same esterification as in Example 3 isconducted, and 33.1 g. (94%) of pale yellow oily 4-cyanophthalimidomethyl ester of chrysanthemum monocarboxylic acid isobtained.

\ O C CO No on and 33.0 g. (89%) of pale yellow oily phthalimidomethylester of pyrethric acid is obtained.

\ o o oo COOCI-I Analysis.Calculated (for C H NO C, 64.68; H, 5.70; N.3.77%. Found: C, 64.60; H, 5.73; N, 3.99%.

EXAMPLE 19 Analysis.-Calculated (for C H NO C, 70.36; H, 6.79; N, 4.10%.Found: C, 70.33; H, 6.87; N, 4.17%.

EXAMPLE 20 A mixture of 20.5 g. (0.1 mole) ofN-(y-hydroxypropy1)phthalimide, 60 g. of pyridine and 50 ml. of drytoluene, is cooled with ice, and a solution of 19 g. of chrysanthemummonocarboxylic acid chloride in 50 ml. of toluene is added thereto. Themixture is treated as 8 in Example 3, and 32.6 g. (92%) of palo yellowoily -(phthalimido)-propyl ester of chrysanthemum monooarboxylic acid isobtained.

Analysis.Calculated (for C H NO C, 70.96; H, 7.09; N, 3.94%. Found: C,70.90; H, 7.18; N, 3.74%.

EXAMPLE 21 A mixture of 16.3 g. (0.1 mole) of N-hydroxyphthalimido, 50g. of pyridine and 40 ml. of dry toluene, is treated with chrysanthemummonocarboxylic acid chloride as in Example 3, and 30.0 g. (96.0%) ofphthalamide ester (anhydride) of chrysanthemum monocarboxylic acid isobtained. A recrystallization from ligroin yields colorless needles,M.P. 7075 C.

Analysisr-Calculat ed (for C H NO C, 68.99; H, 6.11; N, 4.47%. Found: C,69.03; H, 6.25; N, 4.41%.

EXAMPLE 22 Using 19.3 g. (0.1 mole) of N-hydroxymethylthiophthalamideand 19 g. of Chrysanthemum monocarboxylic acid chloride, the sameesterification is conducted, and 32.0 g. (93%) of pink crystallinethiophthalamidomethyl ester of chrysanthemum monocarboxylic acid isobtained.

\ 0 o oo Analysis.Calculated (for C H NO S); C, 66.44; H, 6.16; S,9.34%. Found: C, 66.28; H, 6.09; S, 0.47%.

As mentioned above, the present esters possess superior insecticidalpower, and exhibit rapid knock down and excellent killing effect tohouse flies, mosquitos, cockroaches, etc. Moreover, those esters areespecially useful for sanitary and domestic purposes, because of theirrapid effectiveness and harmlessness (for example, pithalimidomethy-lester of chrysanthemum monocarboxylic acid shows oral toxicity to micein LD value of more than 10 g./kg.). The present esters are suitablyemployed for the preparation of insecticidal compositions which havebroad uses, correlatively with the low cost.

For the formulation of the insecticidal composition containing thepresent compound as the essential ingredient, oil solution, emulsifiableconcentrate, Wettable powder, dust, aerosol, mosquito coil, bait andother preparation, may be formulated using generally employed carriers,diluents or auxiliary agents, according to the method known to thoseskilled in the art in the cases of the formulation of pyrethrum extractand allethrin. If the compound is crystalline, it is preferably employedas a preliminarily prepared solution in an organic solvent, such asacetone, xylene, methylnaphthalene, etc., depending upon the type of theformulation.

If desired, the present esters may be employed for the preparation ofthe insecticidal composition in combination with other insecticidalcomponent, such as pyrethroide, for example, pyrethrum extract andallethrin, organochlorine and onganophosphorus compounds, synergisticagent for pyrethroide, for example, piperonyl 9 l butoxide, sulfoxide,and the like. By combination with EXAMPLE 24 such other ingredient, thepresent insecticidal compositifcfm can be adapted to broader uses withmore increased e ect.

Concretely speaking, the present esters may be blended with at least oneof pyrethrin, allethrin, 0,0-dirnethyl O- (3-methyl-4-nitrophenyl)dithiophosphate, mala-thion, diazinone, dimethoate, 'y-BHC, and others,to yield a pesticidal composition which possesses high insecticidalactivity with rapid effectivity. In such cases, the both components maybe blended in a broad range of proportions, for example, in ratio of0.05:1 to 120.05 by Weight of the ester to another insecticidalcomponent.

The following are the illustrations of the insecticidal compositionscontaining the cyclopropanecarboxylic acid esters according to theinvention and of the insecticidal [Q1t3,1ity(Perce11t) i i iConcentration (Percent) I EXAMPLE 23 ngag 3 2 53? Each 0.4 gram ofphthalimidomethyl ester (I), or

One gram of 4-ch1orophthalimidomethyl ester (III) of chrysanthemummonocarboxylic acid or 3,6-dichlorophthalimidomethyl ester (IV) ofchrysanthemum monocar-boxylic acid was dissolved in 3 ml. of xylene andkerosene was added to the solution to make 100 ml., thereby to yield 1%oil solution.

The 1% oil solution was diluted with kerosene to make solutions ofvarious concentrations. The resulting solutions were sprayed tohouseflies by means of Nagasakas turn-table and the mortality after 24hours was examined.

Following are the results of the experiments:

monothiop'hthalimidornethyl ester II), of crysanthemum 5 gig 2?;2monocarboxylic acid was dissolved in 3 ml. of methyl- 0 524 65.2naphthalene and a refined kerosene was added to the solu- 0 L5 3 0 t-ionto make 100 ml., thereby to yield 0.3% oil solution.

In a glass box of 70 cm. cube, about 30 house flies (adult) wereliberated, and 0.3 ml. of the thus-prepared EXAMPLE 25 oil solution wasuniformly sprayed with an atomizer into the box. Knock down number ofthe house flies ac- 85 g. of xylene and 5 g. of Sorpol 2379 (registeredcording to the lapse of time were observed. Similarly, a trade name ofToho Chemical Company) were mixed 0.4% oil solution prepared usingallethrin was tested for with 10 g. of 4-methylphthalimidomethyl ester(V) or 3- comparison. chloro-4-methoxyphthalimidome-thyl ester (VI) ofchrys- Knock-down ratio of houscflies according to the lapse 0 time(percent) 30sec. 42sec. 1min. 1min., 2min. 2min., 4min. 5min, 8min.

25 sec. 50 sec. sec.

5.4 15.0 33.5 44.1 50.4 56.2 61.8 64.5 68.0 The compound (II) (0.4%

oil solution) as 14.0 33.1 40.0 50.3 57.3 62.0 68.0 68.3 Allethrin (0.4%oil solution) 7.8 15.7 27.2 37.9 48.4 55.8 56.3 67.1 09.2

On the other hand, by use of the same equipment as anthemummonocarboxylic acid. Thus, a homogenous above, a test was made by usingcommon mosquitos. 55 emulsifiable concentrate was obtained. The 0.4% oilpreparation mentioned above was diluted 10 ml. of a solution obtained bydilution of the resultby a refined kerosene to 0.2%, and 0.3 ml. wassprayed. ing 10% emulsifia-ble concentrate was sprayed onto house- Theresults of the test for knock-down ratio of the comflies (adult) in asettling-tower. After 5 seconds, the rnon mosquitos are as follows:shutter was opened and the houseflies were exposed to the Knock-downratio 0 common mosquitos according to the lapse of time (percent) 30sec. 42 sec. 1 min. 1 min., 2 min. 2 min, 4 min. 5 min.. 8 min.

25 sec. sec. 40 sec.

Thecom ound I (0.2

o The compound (II) (0.2%

oi 13.1 25. 3 34. 8 37. 2 44. 0 45. 3 49. 5 58.8 63. 2 Allethrin (0.2%oil) 9. 1 13. 6 13. 6 22. 8 27. 3 40. 9 50.9 63v 6 68. 2

1 ll sprayed air for minutes and were then taken out from the settlingtower. The houseflies were kept in a room at a constant temperature of28 C. and the mortality was examined after 20 hours. Following are theresults of 0.3 g. of phthalimidomethyl ester (VII) of chrysanthemumdicarboxylic acid was dissolved in 3 ml. of methylnaphthalene and, tothis solution, a refined kerosene was added to make the total volume 100ml. Thus, 0.3% oil solution was obtained.

In the same way as in Example 23, knock-down number of houseflies wereexamined. The results of the test were as follows:

12 wherein X X X and X each means a member selected from the groupconsisting of hydrogen halogen, methyl, nitro, methoxy, and cyano; Z isa member selected from the group consisting of oxygen and sulfur; Y is amember selected from the group consisting of a direct linkage, CH --CHCH and CH CH CH and R is a member selected from the group consisting ofmethyl and methoxycarbonyl.

2. Phthalimidomethyl ester of chrysanthemum monocarboxylic acid.

3. A compound selected from the group consisting of4-chlorophthalimidomethyl ester of chrysanthemum monocarboxylic acid, 4bromophthalimidomethyl ester of chrysanthemum monocarboxylic acid,3,6-dichlorophthalimidomethyl ester of chrysanthemum monocarboxylic acidand 3,4,5,6-tetrachlorophthalimidomethyl ester of chrysanthemummonocarboxylic acid.

4. A compound selected from the group consisting of3-nitrophthalimidomethyl ester of chrysanthemum monocarboxylic acid and4-nitrophthalimidomethyl ester of chrysanthemum monocarboxylic acid.

5. 3 bromo-6-nitrophthalimidomethyl ester of chrysanthemummono-carboxylic acid.

6. A compound selected from the group consisting of3-1nethylphthalirnidomethyl ester of chrysanthemum Knock-down ratio ofhouseflies according to the lapse of time (percent) see. 42 sec. 1 min.1 min., 2min. 2 min., 4 min. 5 min.. 8 min.

25 sec. 50 sec. 30 sec.

The compound (VII) (0.3 0 oil 1. 8 8. 7 l7. 1 26. 5 32. 4 41. 3 50. 151. 8 55. 4 Allethriu (0.3% oil) 0 2. 6 9. 0 l4. 2 27. 9 44. 3 54. 3 63.5 78. 9

EXAMPLE 27 monocarboxylic acid and 4-methylphthalimidomethyl ester Twograms of phthaliminomethyl ester of chrysanthemum monocarboxylic acid isdissolved in 10 ml. of acetone, and the solution is mixed with 98 g. of300 mesh (Taylor) tale. The mixture is well blended by a mixer, and theacetone is allowed to evaporate. Thus, a dust preparation containing 2%of the active ingredient is ob- -tained.

Into a settling tower attached with a cage in which about 30 houseflies(adult) are liberated, 100 mg. or 500 mg. of the dust preparation isscattered, and the houseflies are allowed to be exposed to thepreparation as in Example 25. After 20 hours, the mortalities areobserved.

Mg. Mortality (percent) 1000 100.0 500 78.3 Control 2.5

What we claim is: 1. A cyclopropanecarboxylic acid ester of the formula,

References Cited by the Examiner UNITED STATES PATENTS 2,487,106 11/1948Cornwell 260-326 OTHER REFERENCES A Cram et al.: Organic Chemistry,McGraw-Hill Book Co., Inc., New York, 1959, pages -77.

Nefkens: Nature, vol. 193, 1962, pages 974-975.

ALEX MAZEL, Primary Examiner.

MARY U. OBRIEN, Assistant Examiner.

1. A CYCLOPROPANECARBOXYLIC ACID ESTER OF THE FORMULA,